The invention relates to novel substituted 1,3,5-triazines, to processes and novel intermediates for their preparation and to their use as herbicides.
Some substituted 1,3,5-triazines having herbicidal action have already been disclosed (see JP-A 19400/1961, U.S. Pat. Nos. 3,816,419, 3,932,167, JP-A 192873/1983, WO-A 90/09378). Likewise, the compounds (R)-6-chloro-N-(1-cyclohexyl-ethyl)-Nxe2x80x2-ethyl-1,3,5-triazine-2,4-diamine, (S)-6-chloro-N-(1-cyclohexylethyl)-Nxe2x80x2-ethyl-1,3,5-triazine-2,4-diamine and (R,S)-6-chloro-N-(1-cyclohexyl-ethyl)-Nxe2x80x2-ethyl-1,3,5-triazine-2,4-diamine have already been disclosed in the literature as herbicidally active compounds (cf. Z. Naturforsch., C: Biosc. (1987), 42, 663-669xe2x80x94cited in Chem. Abstracts 107:91770). However, these compounds have hitherto not attained any particular importance.
Substituted cyclohexylalkylamino-1,3,5-triazines may be used as herbcides.
This invention, accordingly, provides novel substituted cyclohexylalkylamino-1,3,5-triazines of the general formula (I) 
in which
A represents CHR3R4 or represents C1-halogenoalkyl-substituted C3-C6-cycloalkyl, C3-C6-alkinyl or C1-C4-cyanoalkyl, where
R3 and R4 simultaneously or independently of one another represent optionally cyano-, halogen- or C1-C4-alkoxy-substituted C1-C6-alkyl, represent C1-C4-halogenoalkyl or represent C3-C7-cycloalkyl which is optionally substituted by nitro, cyano, hydroxyl, halogen, by for its part in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms or by for its part optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms and where the total number of carbon atoms of R3 and R4 is greater than 3,
R1 represents amino, formylamino, represents dialkylaminoalkylideneamino having up to 6 carbon atoms, or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkylcarbonylamino, alkoxycarbonyl-amino or alkylaminocarbonylamino having in each case 1 to 6 carbon atoms in the alkyl groups, and
R2 represents in each case optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms or represents optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms.
Preferred substituents or ranges of the radicals present in the formulae listed above and below are described below.
A preferably represents CHR3R4, preferably represents C1-halogenoalkyl-substituted C5-C6-cycloalkyl, preferably represents 1,1-dimethyl-2-propinyl or preferably represents 1-cyano-1-methylethyl, where
R3 and R4 preferably simultaneously or independently represent optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted C1-C5-alkyl, represent C1-C3-halogenoalkyl or represent C3-C6-cycloalkyl which is optionally substituted by nitro, cyano, hydroxyl, fluorine, chlorine, bromine, by for its part in each case optionally cyano-, fluorine-, chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or by for its part in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, and where the total number of carbon atoms of R3 and R4 is greater than 3,
R1 preferably represents amino, formylamino, dimethylaminomethyleneamino or diethylaminomethyleneamino, or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted acetyl-amino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, n- or i-propylaminocarbonylamino.
R2 preferably represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
A particularly preferably represents CHR3R4, represents trifluoromethyl-substituted cyclohexyl, represents 1,1-dimethyl-2-propinyl or represents 1-cyano-1-methylethyl, where
R3 and R4 particularly preferably simultaneously or independently represent in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl, represent 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, 3-fluoropropyl or 3-chloropropyl or represent cyclopentyl or cyclohexyl, where the cycloalkyl radicals are optionally substituted by hydroxyl, fluorine, chlorine, by for its part in each case optionally fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or by for its part in each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-substituted cyclohexyl, and where the total number of carbon atoms of R3 and R4 is greater than 3,
R1 particularly preferably represents amino, formylamino, dimethylaminomethyleneamino, acetylamino or propionylamino.
R2 particularly preferably represents in each case optionally fluorine-, chlorine-, methoxy-, ethoxy-substituted methyl, ethyl, n- or i-propyl.
A very particularly preferably represents CHR3R4, represents trifluoromethyl-substituted cyclohexyl, represents 1,1-dimethyl-2-propinyl or represents 1-cyano-1-methylethyl, where
R3 and R4 very particularly preferably simultaneously or independently represent methyl, ethyl, n- or i-propyl, represent 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, 3-fluoropropyl or 3-chloropropyl or represent cyclopentyl or cyclohexyl and where the total number of carbon atoms of R3 and R4 is greater than 3.
R1 very particularly preferably represents amino, formylamino, ethylcarbonylamino or methylcarbonylamino.
R2 very particularly preferably represents 1-fluoroethyl, difluorochloromethyl, dichloromethyl or 1-fluoro-1-methylethyl.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other as desired, i.e. including combinations between the given preferred ranges.
Preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings listed above as being preferred.
Particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings mentioned above as being particularly preferred.
Very particular preference according to the invention is given to those compounds of the formula (I) which contain a combination of the meanings listed above as being very particularly preferred.
Halogen represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Saturated or unsaturated hydrocarbon radicals, such as alkyl,xe2x80x94also in combination with heteroatoms, such as in alkoxyxe2x80x94are in each case straight-chain or branched as far as this is possible. C1-C6-alkyl represents, for example, methyl, ethyl, n- and i-propyl, n-, s-, i- or t-butyl, n-, i-, t- or neo-pentyl, n-, i-, s-, t- or neo-hexyl inter alia.
Likewise, alkinyl radicals can in each case be straight-chain or branched. C2-C6-alkinyl represents, for example, ethinyl, 1-propinyl, 2-propinyl, 1-methyl-2-propinyl, 1,1-dimethyl-2-propinyl, 1-ethyl-2-propinyl inter alia.
The following radicals may be mentioned by way of example for optionally substituted cycloalkyl radicals: cyclopropyl, 2-methylcyclopropyl, 2-chlorocyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2-fluorocyclopentyl, cyclohexyl, 4-methylcyclohexyl, 2-fluorocyclohexyl, cycloheptyl etc.
Halogenoalkyl radicals which may be mentioned by way of example are: fluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl, 3-fluoropropyl, 3-chloropropyl etc.
Cyano-substituted alkyl radicals which may be mentioned by way of example are: cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 3-cyanopropyl, 1-cyanopropyl, 1-cyano-1-methylethyl, 4-cyanobutyl etc.
Alkylcarbonyl radicals which may be mentioned by way of example are: methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl, n-butylcarbonyl etc.
Optionally substituted radicals can be mono- or polysubstituted, and in the case of polysubstitution, the substituents can be identical or different.
The compounds of the general formula (I) according to the invention contain at least one asymmetrically substituted carbon atom, and they can therefore be present in different enantiomeric (R- and S-configured forms) or diasteromeric forms. The invention relates both to the different possible individual enantiomeric or stereoisomeric forms of the compounds of the general formula (I) and to the mixtures of these isomeric compounds.
The novel substituted 1,3,5-triazines of the general formula (I) have interesting biological properties. In particular, they have strong herbicidal action.
Examples of compounds of the general formula (I) are listed in Table 1 below.
The novel substituted 1,3,5-triazines of the general formula (I) are obtained when
(a) biguanides of the general formula (II) 
xe2x80x83in which
A and R1 are each as defined above,
and/or acid adducts of compounds of the general formula (II)
are reacted with alkoxycarbonyl compounds of the general formula (III)
R2xe2x80x94COxe2x80x94OR5xe2x80x83xe2x80x83(III),
xe2x80x83in which
R2 is as defined above and
R5 represents alkyl,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent
and if appropriate the resulting compounds of the general formula (I) are subjected to further conversions within the scope of the definition of the substituents, by customary methods,
or
(b) 1,3,5-triazines of the formula (Ia) in which R1 represents amino 
xe2x80x83where A and R2 are as defined above,
are reacted with carbonyl halides of the general formula (IV)
R6X2xe2x80x83xe2x80x83(IV)
xe2x80x83where
R6 represents formyl or represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkylcarbonyl having in each case 1 to 6 carbon atoms in the alkyl group and X2 represents chlorine or bromine,
in the presence of a diluent and, if appropriate, in the presence of a base,
or (c) the compounds of the general formula (Ia) in which R1 represents amino are reacted with carboxylic anhydrides of the general formula (V)
R6OR6xe2x80x83xe2x80x83(V),
xe2x80x83where
R6 is as defined above,
in the presence of a diluent and, if appropriate, in the presence of a base,
or (d) the compounds of the general formula (Ia) in which R1 represents amino are reacted with carboxylic esters of the general formula (VI)
R6OR5xe2x80x83xe2x80x83(VI),
xe2x80x83where
R5 and R6 are each as defined above,
in the presence of a diluent and, if appropriate, in the presence of a base,
or (e) the compounds of the general formula (Ia) in which R1 represents amino are reacted with carboxylic acids of the general formula (VII)
R6OHxe2x80x83xe2x80x83(VII),
xe2x80x83where
R6 is as defined above,
in the presence of a diluent and, if appropriate, in the presence of a condensing agent.
Using, for example, 1-(1-cyclohexyl-ethyl)-biguanide and methyl trifluoroacetate as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following formula scheme: 
Using, for example, the hydrogen chloride adduct of 1-(1-ethylpropyl)-biguanide and methyl 1-fluoro-1-methylacetate as starting material, the course of the reaction in the process (a) according to the invention can be illustrated by the following formula scheme: 
Using, for example, N-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine and acetyl chloride as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following formula scheme: 
Using, for example, N-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine and acetic anhydride as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following formula scheme: 
Using, for example, N-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine and ethyl acetate as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following formula scheme: 
Using, for example, N-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine and acetic acid as starting materials, the course of the reaction in the process (e) according to the invention can be illustrated by the following formula scheme: 
The formula (II) provides a general definition of the biguanides to be used as starting materials in the process according to the invention for preparing compounds of the general formula (I). In the general formula (II), A preferably or in particular has those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention as being preferred or as being particularly preferred for A.
Suitable acid adducts of compounds of the formula (II) are their addition products with protic acids, such as, for example, with hydrogen chloride, hydrogen bromide, sulphuric acid, methanesulphonic acid, benzenesulphonic acid and p-toluenesulphonic acid.
The starting materials of the general formula (II) have not yet been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
Among the intermediates of the general formula (II), particular mention may be made of the subgroup in which A represents CHR3R4,
where R3 represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted C1-C6-alkyl and R4 represents cyclohexyl which is optionally substituted by nitro, cyano, hydroxyl, halogen, by for its part in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms or by for its part optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,
and where R3 preferably represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl, represents 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, 3-fluoropropyl or 3-chloropropyl and R4 preferably represents cyclohexyl which is optionally substituted by hydroxyl, fluorine, chlorine, by for its part in each case optionally fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or by for its part in each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-substituted cyclohexyl.
R6 in all formulae of the compounds according to the invention preferably represents formyl or C1-C3-alkylcarbonyl and particularly preferably represents formyl, methylcarbonyl or ethylcarbonyl.
The novel biguanides of the general formula (II) are obtained when substituted amines of the general formula (VIII)
Axe2x80x94NH2xe2x80x83xe2x80x83(VIII),
in which
A is as defined above,
and/or acid adducts of compounds of the general formula (VIII), such as, for example, the hydrochlorides
are reacted with cyanoguanidine (xe2x80x9cdicyanodiamidexe2x80x9d) of the formula (IX) 
if appropriate in the presence of a reaction auxiliary, such as, for example, hydrogen chloride, and if appropriate in the presence of a diluent, such as, for example, n-decane or 1,2-dichloro-benzene, at temperatures between 100xc2x0 C. and 200xc2x0 C. (cf. the Preparation Examples).
After their preparation, the biguanides of the general formula (II) can also be employed directly, without intermediate isolation, for preparing the compounds of the general formula (I) by the process according to the invention.
Hydrochlorides according to the invention of the compounds of the general formula (II) which may be mentioned by way of example are: 1-methylbutylbiguanide hydrochloride, 1,2-dimethylpropylbiguanide hydrochloride, 1,3-dimethylbutylbiguanide hydrochloride, 1-ethylpropylbiguanide hydrochloride, 1-ethylbutylbiguanide hydrochloride, 1-ethyl-2-methylpropylbiguanide hydrochloride, 1-ethylpentylbiguanide hydrochloride, 1-ethyl-2-methylbutylbiguanide hydrochloride, 1-ethyl-3-methylbutylbiguanide hydrochloride, 1-ethyl-2,2-dimethylpropylbiguanide hydrochloride, 1-cyclopropylpropylbiguanide hydrochloride, 1-cyclo-pentylpropylbiguanide hydrochloride, 1-cyclohexylpropylbiguanide hydrochloride, 1-propylbutylbiguanide hydrochloride, 1-isopropylbutylbiguanide hydrochloride, 1-propylpentylbiguanide hydrochloride, 1-isopropyl-2-methylpropylbiguanide hydrochloride, 1-isopropylpentylbiguanide hydrochloride, 1-butylpentylbiguanide hydrochloride, 1-isobutylpentylbiguanide hydrochloride, 1,5-dimethylhexylbiguanide hydrochloride, 1-pentylhexylbiguanide hydrochloride, 1-ethyl-3-fluoropropylbiguanide hydrochloride, 3-chloro-1-ethylpropylbiguanide hydrochloride, 1-ethyl-2-fluoropropylbiguanide hydrochloride, 1-ethyl-4-fluorobutylbiguanide hydrochloride, 4-chloro-1-ethylbutylbiguanide hydrochloride, 2-trifluoromethylcyclohexylbiguanide hydrochloride, 3-trifluoromethylcyclohexyl-biguanide hydrochloride, 4-trifluoromethylcyclohexylbiguanide hydrochloride, 1,1-dimethyl-2-propinylbiguanide hydrochloride, 1-cyano-1-methylethylbiguanide hydrochloride etc.
The substituted amines of the general formula (VIII) required as precursors are known and/or can be prepared by processes known per se (cf. Bull. Soc. Chim. France 1952, 276-279; loc. cit. 1953, 974-981; Bull. Chem. Soc. Japan 57 (1984), 1570-1575; J. Am. Chem. Soc. 76 (1954), 4564-4570; loc. cit. 80 (1958), 5270-5272, JIKKEN KAGAKU KOUZA (Lectures of experimental chemistry), edited by the Chemical Society of Japan, Vol. 14, p. 1339 (1978) published by Maruzen; J. Am. Chem. Soc., 75, 3212 (1953); J. Am. Chem. Soc., 78, 860 (1956); J. Am. Chem. Soc., 66, 1517 (1944); Angew. Chem. Int. Ed., 7, 919 (1968); J. Chem. Soc., 2348 (1926); Synthesis, 717 (1980); Org. React., 3, 267 (1946); J. Chem. Soc., 267 (1941); Org. React., 3, 307 (1946); Org. React., 3, 337 (1946); J. Org. Chem. USSR, 16, 1031 (1980); Farmaco Ed. Sci., 22, 1037 (1967); J. Biol. Chem., 120, 772 (1937); WO 92/12121; EP-A 176327; CS-B233428; DE-A 2843480 etc.).
Hydrochlorides of the compounds of the general formula (VIII) according to the invention which may be mentioned by way of example are:
1-methylbutylamine hydrochloride, 1,2-dimethylpropylamine hydrochloride, 1,3-dimethylbutylamine hydrochloride, 1-ethylpropylamine hydrochloride, 1-ethylbutylamine hydrochloride, 1-ethyl-2-methylpropylamine hydrochloride, 1-ethylpentylamine hydrochloride, 1-ethyl-2-methylbutylamine hydrochloride, 1-ethyl-3-methylbutylamine hydrochloride, 1-ethyl-1,1-dimethylpropylamine hydrochloride, 1-cyclopropylpropylamine hydrochloride, 1-cyclopentylpropylamine hydrochloride, 1-cyclohexylpropylamine hydrochloride, 1-propylbutylamine hydrochloride, 1-isopropylbutylamine hydrochloride, 1-propylpentylamine hydrochloride, 1-isopropyl-2-methylpropylamine hydrochloride, 1-propylpentylamine hydrochloride, 1-isopropyl-2-methylpropylamine hydrochloride, 1-isopropylpentylamine hydrochloride, 1-butylpentylamine hydrochloride, 1-isobutylpentylamine hydrochloride, 1,5-dimethylhexylamine hydrochloride, 1-pentylhexylamine hydrochloride, 1-ethyl-3-fluoropropylamine hydrochloride, 3-chloro-1-ethylpropylamine hydrochloride, 1-ethyl-2-fluoropropylamine hydrochloride, 1-ethyl-4-fluorobutylamine hydro-chloride, 4-chloro-1-ethylbutylamine hydrochloride, 2-trifluoromethylcyclohexyl-amine hydrochloride, 3-trifluoromethylcyclohexylamine hydrochloride, 4-trifluoro-methylcyclohexylamine hydrochloride, 1,1-dimethyl-2-propinylamine hydrochloride, 1-cyano-1-methylethylamine hydrochloride etc.
The compound of the formula (IX) is a synthesis compound known in organic chemistry.
The formula (III) provides a general definition of the alkoxycarbonyl compounds further to be used as starting materials in the process according to the invention for preparing compounds of the general formula (I). In the general formula (III), R2 preferably or in particular has that meaning which has already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention as being preferred or as being particularly preferred for R2; R5 preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
The starting materials of the general formula (III) are known chemicals for synthesis (see, for example, DE-A 4131242, EP-A 850911, EP-A 468681, JP-A 301844/1993, J. Org. Chem., 33, 4279 (1968) etc.). Examples of such compounds which may be mentioned are: methyl 1-fluoropropionate, ethyl 1-fluoropropionate, propyl 1-fluoropropionate, butyl 1-fluoropropionate, methyl 1-fluoro-1-methylpropionate, ethyl 1-fluoro-1-methylpropionate, propyl 1-fluoro-1-methylpropionate, butyl 1-fluoro-1-methylpropionate, etc.
The compounds of the general formula (Ia) which are used as starting compounds in the processes according to (b), (c), (d) and (e) are novel and can be prepared, for example, as a subgroup of compounds of the formula (I) by the process according to (a). Examples of such compounds which may be mentioned are: N-(1-methylbutyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine, N-(1,2-dimethylpropyl-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine, N-(1,3-dimethylbutyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine, N-(1,5-dimethylhexyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine, N-(1-ethylpropyl)-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine, N-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine, N-(1-ethylbutyl)-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine, N-(1-ethylbutyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine, N-(1-ethyl-2-methylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine, N-(1-ethylpentyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine etc.
The compounds of the formulae (IV), (V), (VI) and (VII) are known synthesis compounds of organic chemistry. In these compounds, R6 preferably represents formyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl and particularly preferably represents formyl, methylcarbonyl, ethylcarbonyl, acetyl or propionyl. R6 very particularly preferably represents formyl, ethylcarbonyl, methylcarbonyl. Compounds of the general formula (IV) which may be mentioned by way of example are: acetyl chloride, acetyl bromide, propionyl chloride.
Compounds of the general formula (V) which may be mentioned by way of example are: acetic anhydride and propionic anhydride.
Compounds of the general formula (VI) which may be mentioned by way of example are: methyl formate, ethyl formate, n-propyl formate, n-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate and n-butyl propionate.
Compounds of the general formula (VII) which may be mentioned by way of example are: formic acid, acetic acid and propionic acid.
The process according to the invention according to (a) for preparing the compounds of the general formula (I) is preferably carried out using a diluent. Suitable diluents for carrying out the process according to the invention are, in addition to water, especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated, hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxymethane (DME), tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, methyl ethyl ketone (MEK), butanone, methyl isopropyl ketone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethylsulphoxide; alcohols, such as methanol, ethanol, n- or i-propanol, butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
Suitable reaction auxiliaries for the process according to the invention are, in general, the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide, or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-diethylaniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 1,1,4,4-tetramethylmethylenediamine (TMEDA), 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU), and also organolithium compounds, such as, for example, methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, lithium diisopropylamide, n-butyllithium DABCO, n-butyllithium. DBU, n-butyllithium TMEDA etc.
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0xc2x0 C. and 150xc2x0 C., preferably between 10xc2x0 C. and 120xc2x0 C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
For carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts, 1 mol of a compound of the general formula (II) can be reacted, for example, with 1-2 mol of a compound of the general formula (III) in the presence of a base, for example 1-2 mol of sodium ethoxide, in the diluent ethanol. However, it is also possible to employ a relatively large excess of one of the components. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred at the required temperature for a plurality of hours. Work-up is carried out by customary methods (cf. the Preparation Examples).
The process according to the invention according to (b), (c), (d) or (e) for preparing the compounds of the general formula (I) is preferably carried out using a diluent. Suitable diluents for carrying out the process according to the invention are, in addition to water, especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated, hydrocarbons, such as, for example, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride; ethers, such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxymethane (DME), tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, methyl ethyl ketone (MEK), butanone, methyl isopropyl ketone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl-sulphoxide; alcohols, such as methanol, ethanol, n- or i-propanol, butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
Suitable reaction auxiliaries for the processes according to the invention according to (b), (c) or (d) are, in general, the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide, or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, N,N-dimethyl-aniline, N,N-diethylaniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 1,1,4,4-tetramethylmethylenediamine (TMEDA), 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]-non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).
The process according to the invention according to (e) is preferably carried out in the presence of a condensing agent. Examples of such condensing agents which may be mentioned are: dicyclohexylcarbodiimide, acetic anhydride, thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, aluminium oxide, silicon tetrachloride, titanium tetrachloride etc.
When carrying out the processes according to the invention according to (b), (c), (d) or (e), the reaction temperatures can be varied within a relatively wide range. In general, the processes are carried out at temperatures between 0xc2x0 C. and 150xc2x0 C., preferably between 0xc2x0 C. and 120xc2x0 C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
For carrying out the process according to the invention according to (b), the starting materials are generally employed in approximately equimolar amounts, 1 mol of a compound of the general formula (Ia) can be reacted, for example, with 0.8-2.0 mol of a compound of the general formula (IV) in the presence of a base, for example 1-3 mol of triethylamine. However, it is also possible to employ a relatively large excess of one of the components.
For carrying out the process according to the invention according to (c), the starting materials are generally employed in approximately equimolar amounts, 1 mol of a compound of the general formula (Ia) can be reacted, for example, with 0.8-2.0 mol of a compound of the general formula (V) in the presence of a base, for example 1-3 mol of triethylamine. However, it is also possible to employ a relatively large excess of one of the components.
For carrying out the process according to the invention according to (d), the starting materials are generally employed in approximately equimolar amounts, 1 mol of a compound of the general formula (Ia) can be reacted, for example, with 0.8-2.0 mol of a compound of the general formula (VI) in the presence of a base, for example 1-3 mol of sodium methoxide. However, it is also possible to employ a relatively large excess of one of the components.
For carrying out the process according to the invention according to (e), the starting materials are generally employed in approximately equimolar amounts, 1 mol of a compound of the general formula (Ia) can be reacted, for example, with 0.8-2.0 mol of a compound of the general formula (IV) in the presence of a condensing agent, for example dicyclohexylcarbodiimide. However, it is also possible to employ a relatively large excess of one of the components.
The active compounds according to the invention are particuliarly suitable for use as defoliants, desiccants, haulmkillers and, especially, as weedkillers. Weeds, in the broadest sense, are to be understood as all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used. The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera, Aegilop, Phalaris.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
In a use form that is emphasized here, the active compounds according to the invention can also be used in connection with transgenic plants. In this case, a synergistic effect was observed.
The active compounds according to the invention are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the active compounds according to the invention can be employed for controlling weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pastures, and for the selective control of weeds in annual crops.
The compounds of the formula (I) according to the invention have strong herbicidal activity and a broad activity spectrum when used on the soil and on above-ground parts of the plants. To a certain extent, they are also suitable for the selective control of monocotyledonous and dicotyledonous weeds, in particular in monocotyledonous crops, both pre- and post-emergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifiers and/or dispersants and/or foam-formers.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. Suitable liquid solvents are mainly: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, mineral or vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, ready mixes or tank mixes being possible.
Examples of known herbicides which are suitable for the mixtures are acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzobicyclon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazone, chlorimuron(-ethyl), chlornitrofen, chlorosulfuron, chlortoluron, cinidone(-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamide, dimexyflam, dinitramine, diphenamide, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop(-P-ethyl), fentrazamide, flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, florasulam, fluazifop(-P-butyl), fluazolate, flucarbazone, flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, glufosinate (-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron(-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, thiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil conditioners is also possible.
To improve compatibility with crop plants, it is also possible to mix the compounds of the general formula (I) with one or more safeners, and the safener 1-(xcex1,xcex1-dimethylbenzyl)-3-p-tolylurea may be mentioned as an example here.
The active compounds may be applied as such, in the form of their formulations or of the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are applied in the customary manner, for example by pouring, spraying, atomizing, broadcasting.
The active compounds according to the invention can be applied either before or after plant emergence. They may also be incorporated into the soil prior to planting.
The amount of active compound applied can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the application rates are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.